U.S. patent application number 10/660079 was filed with the patent office on 2004-03-18 for fire-protection coating.
This patent application is currently assigned to Clariant GmbH. Invention is credited to Thewes, Volker, Zurstrassen, Andrea.
Application Number | 20040051087 10/660079 |
Document ID | / |
Family ID | 31896126 |
Filed Date | 2004-03-18 |
United States Patent
Application |
20040051087 |
Kind Code |
A1 |
Thewes, Volker ; et
al. |
March 18, 2004 |
Fire-protection coating
Abstract
The invention relates to a fire-protection coating which forms
an insulating layer and is based on substances which, in the event
of a fire, form a foam layer and form carbon, on film-forming
binders, on blowing agents, and on conventional auxiliaries and
additives, which comprises a phosphinic salt of the formula (I)
and/or a diphosphinic salt of the formula (II), and/or their
polymers, 1 where R.sup.1, R.sup.2 are identical or different and
are C.sub.1-C.sub.6-alkyl, linear or branched and/or aryl; R.sup.3
is C.sub.1-C.sub.10-alkylene, linear or branched,
C.sub.6-C.sub.10-arylene, -alkylarylene, or -arylalkylene; M is Mg,
Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn, Li, Na, K,
and/or a protonated nitrogen base; m is from 1 to 4; n is from 1 to
4; x is from 1 to 4.
Inventors: |
Thewes, Volker; (Erftstadt,
DE) ; Zurstrassen, Andrea; (Koeln, DE) |
Correspondence
Address: |
Clariant Corporation
Industrial Property Department
4000 Monroe Road
Charlotte
NC
28205
US
|
Assignee: |
Clariant GmbH
|
Family ID: |
31896126 |
Appl. No.: |
10/660079 |
Filed: |
September 11, 2003 |
Current U.S.
Class: |
252/606 ;
524/126; 524/133; 524/135 |
Current CPC
Class: |
C09D 5/185 20130101 |
Class at
Publication: |
252/606 ;
524/126; 524/133; 524/135 |
International
Class: |
C08L 001/00; C09K
021/00 |
Foreign Application Data
Date |
Code |
Application Number |
Sep 17, 2002 |
DE |
10243231.7 |
Claims
1. A fire-protection coating which forms an insulating layer and is
based on substances which, in the event of a fire, form a foam
layer and form carbon, on film-forming binders, on blowing agents,
and on conventional auxiliaries and additives, which comprises a
phosphinic salt of the formula (I) and/or a diphosphinic salt of
the formula (II), and/or their polymers, 4 5where R.sup.1, R.sup.2
are identical or different and are C.sub.1-C.sub.6-alkyl, linear or
branched and/or aryl; R.sup.3 is C.sub.1-C.sub.10-alkylene, linear
or branched, C.sub.6-C.sub.10-arylene, -alkylarylene, or
-arylalkylene; M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi,
Sr, Mn, Li, Na, K, and/or a protonated nitrogen base; m is from 1
to 4; n is from 1 to 4; x is from 1 to 4.
2. The fire-protection coating which forms an insulating layer, as
claimed in claim 1, wherein M is calcium, aluminum, or zinc.
3. The fire-protection coating which forms an insulating layer, as
claimed in claim 1 or 2, wherein R.sup.1 and R.sup.2 are identical
or different and are C.sub.1-C.sub.6-alkyl, linear or branched,
and/or phenyl.
4. The fire-protection coating which forms an insulating layer, as
claimed in one or more of claims 1 to 3, wherein R.sup.1 and
R.sup.2 are identical or different and are methyl, ethyl, n-propyl,
isopropyl, n-butyl, tert-butyl, n-pentyl and/or phenyl.
5. The fire-protection coating which forms an insulating layer, as
claimed in one or more of claims 1 to 4, wherein R.sup.3 is
methylene, ethylene, n-propylene, isopropylene, n-butylene,
tert-butylene, n-pentylene, n-octylene or n-dodecylene; phenylene
or naphthylene; methylphenylene, ethylphenylene,
tert-butylphenylene, methylnaphthylene, ethylnaphthylene or
tert-butylnaphthylene; phenylmethylene, phenylethylene,
phenylpropylene or phenylbutylene.
6. The fire-protection coating which forms an insulating layer, as
claimed in one or more of claims 1 to 5, which comprises from 5 to
30 parts by weight of film-forming binder, from 10 to 50 parts by
weight of substance which forms a foam layer, from 5 to 25 parts by
weight of a substance which forms carbon, from 5 to 25 parts by
weight of a blowing agent, and from 10 to 50 parts by weight of
conventional auxiliaries and additives, and from 1 to 10 parts by
weight of aluminium diethylphosphinate.
7. The fire-protection coating which forms an insulating layer, as
claimed in one or more of claims 1 to 6, which comprises from 10 to
25 parts by weight of film-forming binder, from 15 to 40 parts by
weight of substance which forms a foam layer, from 7 to 15 parts by
weight of a substance which forms carbon, from 7 to 15 parts by
weight of a blowing agent, and from 20 to 40 parts by weight of
conventional auxiliaries and additives, and from 2 to 5 parts by
weight of aluminium diethylphosphinate.
8. The fire-protection coating which forms an insulating layer, as
claimed in one or more of claims 1 to 7, wherein the film-forming
binders present comprise homopolymers based on vinyl acetate,
copolymers based on vinyl acetate, ethylene, and vinyl chloride,
copolymers based on vinyl acetate and on the vinyl ester of a
long-chain, branched carboxylic acid, copolymers based on vinyl
acetate and di-n-butyl malate, copolymers based on vinyl acetate
and esters of acrylic acid, copolymers based on styrene and esters
of acrylic acid, and/or copolymers based on esters of acrylic acid,
vinyltoluenel/acrylol copolymer, styrene/acrylate polymers,
vinyl/acrylate copolymers, self-crosslinking polyurethane
dispersions
9. The fire-protection coating which forms an insulating layer, as
claimed in one or more of claims 1 to 8, wherein the foam-forming
substances present comprise ammonium salts of phosphoric acids
and/or polyphosphoric acids.
10. The fire-protection coating which forms an insulating layer, as
claimed in one or more of claims 1 to 9, wherein the carbon-forming
substances present comprise carbohydrates.
11. The fire-protection coating which forms an insulating layer, as
claimed in claim 7, wherein the carbohydrates used comprise
pentaerythritol, dipentaerythritol, tripentaerythritol and/or
polycondensates of pentaerythritol.
12. The fire-protection coating which forms an insulating layer, as
claimed in one or more of claims 1 to 11, wherein the auxiliaries
and additives present comprise glass fibers, mineral fibers,
kaolin, talc, aluminum oxide, aluminum hydroxide, magnesium
hydroxide, precipitated silicas, silicates and/or pulverulent
celluloses.
13. The fire-protection coating which forms an insulating layer, as
claimed in one or more of claims 1 to 12, wherein the blowing
agents present comprise melamine and/or guanidine, or else their
salts, and/or dicyandiamides.
14. The fire-protection coating which forms an insulating layer, as
claimed in claim 13, wherein the melamine salts used comprise
melamine phosphate, melamine cyanurate, melamine borate, melamine
silicate, and the guanidine salt used comprises guanidine
phosphate.
15. The fire-protection coating which forms an insulating layer, as
claimed in one or more of claims 1 to 14, which also comprises
melamine polyphosphate.
Description
[0001] The invention relates to a fire-protection coating which
forms an insulating layer and is based on substances which, in the
event of a fire, form a foam layer and form carbon, on film-forming
binders, on blowing agents, and on conventional auxiliaries and
additives.
[0002] Fire-protection layers which form an insulating layer, also
termed intumescent coatings, foam when exposed to the type of
temperature occurring in the event of a fire, thus, by virtue of
this foaming of the abovementioned fire-protection coating
preventing, or at least inhibiting, the passage of heat to steel
work, ceilings, walls, cables, pipes, and the like.
[0003] U.S. Pat. No. 4,965,296 A1 describes a flame-retardant
material composed of a flame-retardant coating material and of an
electrically conductive material. The flame-retardant coating
material here is composed of substances which form foam and form
carbon, of a compound which evolves gas, of a film-forming binder,
and of appropriate solvents. Other conventional ingredients may be
present if desired.
[0004] U.S. Pat. No. 4,879,320 describes a similar flame-retardant
composition to which, instead of a conductive material, a ceramic
fiber material has been added.
[0005] U.S. Pat. No. 5,225,464 describes an aqueous intumescent
formulation based on a reaction product of phosphoric acid,
melamine and monoammonium phosphate. This formulation with
pentaerythritol, chlorinated hydrocarbons, and other compounds, in
particular polyvinyl acetate, is intended to provide an improved
intumescent coating material.
[0006] DE 42 18 184 A1 describes an aqueous binder mixture composed
of an aqueous solution and/or dispersion of a combination of a) at
least one NCO prepolymer which has capped isocyanate groups and has
urethane groups and, in the presence of component b), is
dispersible and/or soluble in water, and b) a polyamine component
composed of at least one (cyclo)aliphatic polyamine having at least
two primary and/or secondary amino groups.
[0007] Finally, DE 43 43 668 describes expandable, flame-retardant
coating compositions composed at least of from 4 to 25% by weight
of a film-forming binder, from 10 to 40% by weight of ammonium
polyphosphate, from 8 to 40% by weight of at least one substance
which carbonizes on exposure to heat, from 6 to 25% by weight of a
blowing agent, from 0 to 5% by weight of dispersing agents, and
from 0 to 25% by weight of fillers.
[0008] The aim of the abovementioned fire-protection coatings of
the prior art is to achieve maximum fire-resistance times, using
minimum application quantities.
[0009] An overall disadvantage of the abovementioned
fire-protection coatings is that the foam structures formed in the
event of a fire do not permit an improvement in insulating action,
and that the reaction does not start until temperatures
T.gtoreq.180.degree. C. have been reached.
[0010] An object of the invention which follows is therefore to
provide fire-protection coatings which achieve longer
fire-resistance times for the same application quantity, or achieve
fire-resistance times identical with those of the prior art with a
reduced application quantity.
[0011] It is intended that the reaction start at temperatures
T<180.degree. C.
[0012] This object has been achieved by way of a fire-protection
coating which forms an insulating layer as described at the outset,
which comprises a phosphinic salt of the formula (I) and/or a
diphosphinic salt of the formula (II), and/or their polymers, 2
3
[0013] where
[0014] R.sup.1, R.sup.2 are identical or different and are
C.sub.1-C.sub.6-alkyl, linear or branched and/or aryl;
[0015] R.sup.3 is C.sub.1-C.sub.10-alkylene, linear or branched,
C.sub.6-C.sub.10-arylene, -alkylarylene, or -arylalkylene;
[0016] M is Mg, Ca, Al, Sb, Sn, Ge, Ti, Zn, Fe, Zr, Ce, Bi, Sr, Mn,
Li, Na, K, and/or a protonated nitrogen base;
[0017] m is from 1 to 4;
[0018] n is from 1 to 4;
[0019] x is from 1 to 4.
[0020] M is preferably calcium, aluminium or zinc.
[0021] The protonated nitrogen bases are preferably the protonated
bases of ammonia, melamine, or triethanolamine, in particular
NH.sub.4+.
[0022] R.sup.1, R.sup.2, which are identical or different, are
preferably C.sub.1-C.sub.6-alkyl, linear or branched, and/or
phenyl.
[0023] R.sup.1 and R.sup.2, which are identical or different, are
particularly preferably methyl, ethyl, n-propyl, isopropyl,
n-butyl, tert-butyl, n-pentyl and/or phenyl.
[0024] R.sup.3 is preferably methylene, ethylene, n-propylene,
isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene or
n-dodecylene; phenylene or naphthylene; methylphenylene,
ethylphenylene, tert-butylphenylene, methylnaphthylene,
ethylnaphthylene or tert-butylnaphthylene; phenylmethylene,
phenylethylene, phenylpropylene or phenylbutylene.
[0025] The fire-protection coating which forms an insulating layer
preferably comprises
[0026] from 5 to 30 parts by weight of film-forming binder,
[0027] from 10 to 50 parts by weight of substance which forms a
foam layer,
[0028] from 5 to 25 parts by weight of a substance which forms
carbon,
[0029] from 5 to 25 parts by weight of a blowing agent, and
[0030] from 10 to 50 parts by weight of conventional auxiliaries
and additives, and
[0031] from 1 to 10 parts by weight of phsophinic salt of the
formula (I)
[0032] and/or a diphosphinic salt of the formula (II), and/or their
polymers.
[0033] The fire-protection coating which forms an insulating layer
particularly preferably comprises
[0034] from 10 to 25 parts by weight of film-forming binder,
[0035] from 15 to 40 parts by weight of substance which forms a
foam layer,
[0036] from 7 to 15 parts by weight of a substance which forms
carbon,
[0037] from 7 to 15 parts by weight of a blowing agent, and
[0038] from 20 to 40 parts by weight of conventional auxiliaries
and additives, and
[0039] from 2 to 5 parts by weight of phosophinic salt of the
formula (I) and/or a diphosphinic salt of the formula (II), and/or
their polymers.
[0040] Preference is given to a fire-protection coating which forms
an insulating layer in which the film-forming binders present
comprise
[0041] homopolymers based on vinyl acetate,
[0042] copolymers based on vinyl acetate, ethylene, and vinyl
chloride,
[0043] copolymers based on vinyl acetate and on the vinyl ester of
a long-chain, branched carboxylic acid,
[0044] copolymers based on vinyl acetate and di-n-butyl malate,
[0045] copolymers based on vinyl acetate and esters of acrylic
acid,
[0046] copolymers based on styrene and esters of acrylic acid,
and/or
[0047] copolymers based on esters of acrylic acid,
[0048] vinyltoluenel/acrylol copolymer,
[0049] styrene/acrylate polymers,
[0050] vinyl/acrylate copolymers,
[0051] self-crosslinking polyurethane dispersions.
[0052] Preference is given to a fire-protection coating which forms
an insulating layer and in which the foam-forming substances
present comprise ammonium salts of phosphoric acids and/or
polyphosphoric acids.
[0053] Preference is given to a fire-protection coating which forms
an insulating layer and in which the carbon-forming substances
present comprise carbohydrates.
[0054] Carbohydrates whose use is preferred are pentaerythritol,
dipentaerythritol, tripentaerythritol and/or polycondensates of
pentaerythritol.
[0055] Preference is given to a fire-protection coating which forms
an insulating layer and in which the blowing agents present
comprise melamine and/or guanidine, or else their salts, and/or
dicyandiamides.
[0056] The melamine salts preferably comprise melamine phosphate,
melamine cyanurate, melamine borate, melamine silicate, and the
guanidine salt preferably comprises guanidine phosphate.
[0057] The fire-protection coating which forms an insulating layer
also preferably comprises melamine polyphosphate.
[0058] Preference is given to a fire-protection coating which forms
an insulating layer and in which the auxiliaries and additives
present comprise glass fibers, mineral fibers, kaolin, talc,
aluminum oxide, aluminum hydroxide, magnesium hydroxide,
precipitated silicas, silicates, and/or pulverized celluloses.
[0059] The inventive fire-protection coating (intumescent coating)
is used in the form of a paint which can be applied by brush,
spray, or roller, to protect various substrates, preferably steel,
wood, electrical cables, and pipes.
[0060] In the examples below, intumescent coatings are prepared,
and applied to standard steel sheets, and their effectiveness is
determined. The test for insulating capability was based on DIN
4102.
[0061] The following products were used in the examples:
[0062] .RTM.Pliolite (Solid) (Goodyear, France)
[0063] This is a newtonian, thermoplastic resin based on
vinyltoluene-acrylate copolymer.
[0064] .RTM.Mowilith DM230
[0065] This is a plasticizer-free, aqueous copolymer dispersion of
strength about 50%, composed of vinyl acetate and Versatic
ester.
[0066] .RTM.Exolit AP 462 (Clariant GmbH, Frankfurt am Main)
[0067] This is a microencapsulated ammonium polyphosphate based on
.RTM.Exolit AP 422, prepared by the process of EP-B-0 180 795, and
comprising about 10% by weight of encapsulating material, composed
of a cured melamine-formaldehyde resin.
[0068] .RTM.Exolit AP 422 (Clariant GmbH, Frankfurt am Main) is a
free-flowing, pulverulent, low-water-solubility ammonium
polyphosphate of the formula (NH.sub.4PO.sub.3), where n=20 to
1000, in particular from 500 to 1000. The proportion of the
particles whose particle size is smaller than 45 .mu.m is more than
99%.
EXAMPLE 1
Comparison
[0069] The following substances were mixed with one another and
then appropriately applied to the sheet to be tested:
[0070] 38 parts by weight of .RTM.Exolit AP 462
[0071] 10 parts by weight of .RTM.Pliolite (Solid)
[0072] 8 parts by weight of melamine
[0073] 8 parts by weight of dipentaerythritol
[0074] 8 parts by weight of titanium dioxide
[0075] thickeners, plasticizers and solvents to 100 parts by
weight.
[0076] The fire test on the coated sheet, based on DIN 4102, gave a
reaction starting temperature T=180.degree. C., the application
quantity being 100%.
EXAMPLE 2
Inventive
[0077] The following substances were mixed with one another and
then appropriately applied to the sheet to be tested:
[0078] 32 parts by weight of .RTM.Exolit AP 462
[0079] 10 parts by weight of .RTM.Pliolite (Solid)
[0080] 13 parts by weight of melamine
[0081] 8 parts by weight of dipentaerythritol
[0082] 8 parts by weight of titanium dioxide
[0083] 5 parts by weight of aluminum diethylphosphinate
[0084] thickeners, plasticizers and solvents to 100 parts by
weight.
[0085] The fire test on the coated sheet, based on DIN 4102, gave a
reaction starting temperature T=100.degree. C., the application
quantity being 100%.
EXAMPLE 3
Comparison
[0086] The following substances were mixed with one another and
then appropriately applied to the sheet to be tested:
[0087] 30 parts by weight of .RTM.Exolit AP 422
[0088] 22 parts by weight of .RTM.Mowilith DM230
[0089] 19 parts by weight of melamine
[0090] 13 parts by weight of pentaerythritol
[0091] 5 parts by weight of titanium dioxide
[0092] thickeners, fillers, water, dispersants and preservatives to
100 parts by weight.
[0093] The fire test on the coated sheet, based on DIN 4102, gave a
fire-resistance time of 86 minutes, the application quantity being
100%.
EXAMPLE 4
Inventive
[0094] The following substances were mixed with one another and
then appropriately applied to the sheet to be tested:
[0095] 18 parts by weight of .RTM.Exolit AP 422
[0096] 22 parts by weight of .RTM.Mowilith DM230
[0097] 30 parts by weight of melamine
[0098] 13 parts by weight of pentaerythritol
[0099] 5 parts by weight of titanium dioxide
[0100] 2 parts by weight of aluminum diethylphosphinate
[0101] thickeners, fillers, water, dispersants and preservatives to
100 parts by weight.
[0102] The fire test on the coated sheet, based on DIN 4102 gave a
fire-resistance time of 87 minutes, the application quantity being
80%.
[0103] Using the inventive fire-protection coating, the
fire-resistance time can be increased advantageously, or the
application quantity can be reduced advantageously. There is also a
marked reduction in reaction start temperature.
* * * * *